Conformation of linear polyethylene in 1-chloronaphthalene: Light scattering characterization of polymers. IV

Light scattering measurements were carried out on a linear polyethylene sample NBS 1475 in 1-chloronaphthalene at 135 and 115°C to determine the weight-average molecular weight, the second virial coefficient A₂, and the z-average mean-square radius of gyration. By use of these results, the system is analyzed in terms of the interpenetration function Ψ for A₂. Observed values of A₂ are rather large but the excluded volume is nevertheless relatively small. Such behavior seem to be similar to that of semiflexible polymers. The characteristic ratio C_n,LS as determined by light scattering is found to be almost twice the literature value of 6.7, which was obtained from viscosity measurements. This discrepancy is explained by comparing the theoretical value of the Flory viscosity parameter Φ at the nondraining limit with values calculated from the light scattering results.     

Experimental determination of rheological properties of polydimethylsiloxane

A series of linear polydimethylsiloxane of different molecular weight and with reduced polydispersity were prepared by partial fractionation of commercial products. The rheological functions, i.e. zero shear viscosity (η₀), first and second normal stress coefficients (Ψ₁₀ and Ψ₂₀), of the materials were experimentally measured by conventional rotational rheometers and by a rotation rod apparatus. The relationships between molecular structure (molecular weight and polydispersity index) and rheological functions are presented and discussed on the basis of equations proposed in the literature. Zero shear viscosity data conform to the well-known dependence on a power 3.5 of molecular weight. However, a consistently stronger influence of molecular weight over Ψ₁₀ and Ψ₂₀ is found. The influence of polydispersity over Ψ₁₀ is also analyzed.     

Hyperbranched polyimides prepared by ideal A2+B3 polymerization,non-ideal A2+B3 polymerization and AB2 self-polymerization

In this paper, hyperbranched polyimides having the same repeating unit were synthesized by employing ideal A₂+B₃ polymerization, non-ideal A₂+B₃ polymerization and AB₂ self-polymerization methods. The polymerization behavior, polymer properties were compared for three methods. Hyperbranched polyimides by ideal A₂+B₃ polymerization, non-ideal A₂+B₃ polymerization and AB₂ self-polymerization methods show apparent difference in many physical properties, such as inherent viscosity, glass transition temperature, and film formation behavior etc. The hyperbranched polymers by the non-ideal A₂+B₃ polymerization are suitable for smooth, flexible and self-standing film preparation, which provides useful information for hyperbranched polymers toward self-standing materials.     

Organic and Organometallic Molecular Magnetic Materials—Designer Magnets

Magnets composed of molecular species or polymers and prepared by relatively low-temperature organic synthetic methodologies are a focus of contemporary materials science research. The anticipated properties of such molecular-species-based magnetic materials, particularly in combination with other properties associated with molecules and polymers, may enable their use in future generations of electronic, magnetic, and/or photonic/photronic devices ranging from information storage and magnetic imaging to static and low-frequency magnetic shielding. A tutorial of typical magnetic behavior of molecular materials is presented. The three distinct models (intramolecular spin coupling through orthogonal orbitals in the same spatial region within a molecule/ion, intermolecular spin coupling through pairwise “configuration interaction” between spin-containing moieties, and dipole—dipole, through-space interactions) which enable the design of new molecular-based magnetic materials are discussed. To achieve the required spin couplings for bulk ferro- or ferrimagnetic behavior it is crucial to prepare materials with the necessary primary, secondary, and tertiary structures akin to proteins. Selected results from the worldwide effort aimed at preparing molecular-based magnetic materials by these mechanisms are described. Some organometallic solids comprised of linear chains of alternating metallocenium donors (D) and cyanocarbon acceptors (A) that is, …?D^?+ A^?? D^?+ A^??…?, exhibit cooperative magnetic phenomena. Bulk ferromagnetic behavior was first observed below the critical (Curie) temperature T_c of 4.8 K for [Fe^III(C₅Me₅)₂]^?+ [TCNE]^?? (Me = methyl; TCNE = tetracyanoethylene). Replacement of Fe^III with Mn^III leads to a ferromagnet with a T_c of 8.8 K in agreement with mean-field models developed for this class of materials. Replacement with Cr^III, however, leads to a ferromagnet with a T_c lowered to 3.65 K which is at variance with this model. Extension to the reaction of a vanadium(o) complex with TCNE leads to the isolation of a magnet with a T_c ≈ 400 K, which exceeds the thermal decomposition temperature of the material. This demonstrates that a magnetic material with a T_c substantially above room temperature is achievable in a molecule/organic/polymeric material. Finally, a new class of one-dimensional ferrimagnetic materials based on metalloporphins is discussed.     

Nonadiabatic coupling and diabatic electronic population dynamics on 11A2 and 11B1 states of ozone molecule

In this work, we examine nonadiabatic population dynamics for 1¹B₁ and 1¹A₂ states of ozone molecule (O₃). In O₃, two lowest singlet excited states, ¹A₂ and ¹B₁, can be coupled. Thus, population transfer between them occurs through the seam involving these two states. At any point of the seam (conical intersection), the Born-Oppenheimer approximation breaks down, and it is necessary to investigate nonadiabatic dynamics. We consider a linear vibronic coupling Hamiltonian model and evaluate vibronic coupling constant, diabatic frequencies for three modes of O₃, bilinear and quadratic coupling constants for diabatic potentials, displacements, and Huang-Rhys coupling constants using ab initio calculations. The electronic structure calculations have been performed at the multireference configuration interaction and complete active space with second-order perturbation theory with a full-valence complete active space self-consistent field methods and augmented Dunning's standard correlation-consistent-polarized quadruple zeta basis set to determine ab initio potential energy surfaces for the ground state and first two excited states of O₃, respectively. We have chosen active space comprising 18 electrons distributed over 12 active orbitals. Our calculations predict the linear vibronic coupling constant 0.123 eV. We have obtained the population on the 1¹B₁ and 1¹A₂ excited electronic states for the first 500 fs after photoexcitation.     

The hard-sphere model for linear and regular star polybutadienes

The dilute solution properties of linear, 18-arm, and 270-arm star polybutadienes have been studied in a theta solvent and in a good solvent. Values of the radius of gyration R_G, the second virial coefficient A₂, the intrinsic viscosity [η], and the diffusion coefficient D₀ have been measured for each polymer. The ratios R_T/R_G, R_V/R_G, and R_H/R_G for each type of polymer are used to compare the four dilute solution properties. R_T is termed the “thermodynamic radius.” It is the radius of the hard sphere with the same excluded volume as the polymer coil. R_T is calculated from A₂ by R_T = (3A₂M₂/16ηN_A)^1/3. R_V and R_H are equivalent hard spheres defined for the intrinsic viscosity and translational diffusion coefficient, respectively. R_T/R_G, R_V/R_G, and R_H/R_G increase from about 0.7 for linear polymer coils as the number of arms in the star increases. Values of the ratios for the 18-arm stars are less than the value for the hard-sphere, but the values of the ratios of the 270-arm stars are equal to the hard-sphere limit within experimental error.     

Dynamic nonlinear Jahn–Teller effect of the type E ⊗ ϵ

By applying the projection operator method it is shown that the complicated Hamiltonian of a E ? ? JT system with nonlinear coupling coefficients can be written in terms of two Hamiltonians which are simple to handle and transform according to irreducible representations E, A₁, and A₂ of C_3v point group. A variational approach is then used to calculate the ground state energy, using the Hamiltonian that transforms according to E, as an explicit function of the linear and nonlinear coupling parameters. The energies calculated in the strong coupling limit are finally compared with the corresponding previously calculated energies.     

Metal‐ and solvent‐free,clickable synthesis and postpolymerization functionalization of poly(triazole)s

In this study, a series of linear poly(triazole)s (PTAs) were successfully synthesized by the metal‐ and solvent‐free, thermal click polymerization of diazide and dialkyne (A₂ + B₂) monomers. All click polymerizations proceeded smoothly at 80 °C in an open atmosphere without protection from oxygen and moisture. After being polymerized for 36 h, the crude polymer was further fractionated into three fractions using a multistep precipitation method. By selectively choosing precipitating agents, this process produced poly(triazole) fractions with low polydispersity index (<1.30). The resulting PTAs are soluble in common organic solvents and stable at a temperature up to 320 °C. Furthermore, the methyl benzoate moieties in the main chain can serve as useful building blocks for further postpolymerization functionalization, yielding 1,2,4‐triazole derivatives. This functionalization strategy offers potential for the development of novel triazole‐based materials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Thermomechanical behavior of rubberlike materials

A simple form of nonisothermal free energy function A(λ₁, λ₂, λ₃, T) for rubberlike materials results from postulating that the entropy is a separable symmetric function of the extension ratios λ_i along the principal strain directions and considering the fundamental properties of rubberlike materials, i.e., that rubber elasticity is associated primarily with changes in entropy and the variation of elastic tension with changes in temperature is linear. The explicit representation of A is reduced to the Valanis-Landel strain energy function for isothermal cases.     

Composite tribological materials based on molybdenum disulfide nanoparticles and polytetrafluoroethylene microgranules

Tribological materials based on molybdenum disulfide nanoparticles localized on the surface of ultradispersed polytetrafluoroethylene were prepared. The composition and properties of the new composite materials were studied. Introduction of ultradispersed additives based on polytetrafluoroethylene with MoS₂ and on polytetrafluoroethylene and nanodiamonds prepared by detonation synthesis (taken as reference samples) decreases the viscosity of MS-20 aviation oil. The dependence of the friction coefficient on the Sommerfeld number for the composites obtained was examined. Introduction of additives leads to a decrease in the friction coefficient with increasing linear sliding velocity, in contrast to the initial oil for which the trend is opposite. The dependence of the friction coefficient on the concentration of additives in the initial oil was demonstrated. Modification of polytetrafluoroethylene microgranules with 3 wt % MoS₂ nanoparticles allows the amount of additive to the oil to be considerably reduced.     

Hyperbranched polymers as scaffolds for multifunctional reversible addition–fragmentation chain‐transfer agents: A route to polystyrene‐core‐polyesters and polystyrene‐block‐poly(butyl acrylate)‐core‐polyesters

Polydisperse hyperbranched polyesters were modified for use as novel multifunctional reversible addition–fragmentation chain‐transfer (RAFT) agents. The polyester‐core‐based RAFT agents were subsequently employed to synthesize star polymers of n‐butyl acrylate and styrene with low polydispersity (polydispersity index < 1.3) in a living free‐radical process. Although the polyester‐core‐based RAFT agent mediated polymerization of n‐butyl acrylate displayed a linear evolution of the number‐average molecular weight (M_n) up to high monomer conversions (>70%) and molecular weights [M_n > 140,000 g mol^?1, linear poly(methyl methacrylate) equivalents)], the corresponding styrene‐based system reached a maximum molecular weight at low conversions (≈30%, M_n = 45,500 g mol^?1, linear polystyrene equivalents). The resulting star polymers were subsequently used as platforms for the preparation of star block copolymers of styrene and n‐butyl acrylate with a polyester core with low polydispersities (polydispersity index < 1.25). The generated polystyrene‐based star polymers were successfully cast into highly regular honeycomb‐structured microarrays. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3847–3861, 2003     

Photoactive liquid crystalline polymers: A comprehensive study of linear and hyperbranched polymers synthesized by A2B2, A2B3, A3B2, and A3B3 approaches

A series of linear and hyperbranched polyester epoxies, with varied structural parameters such as kinked structure and different dendritic architectures, were synthesized by A₂ + B₂, A₂ + B₃, A₃ + B₂, and A₃ + B₃ approaches. The structures of synthesized monomers and polymers were confirmed by Fourier transform infrared, ¹H NMR, and ¹³C NMR spectroscopic techniques. The effect of varied structural parameters on phase behavior and photoresponsive properties was investigated by using differential scanning calorimeter, thermal optical polarized microscope, UV–visible spectroscopy, photoviscosity, and refractive index studies. The transition temperatures of hyperbranched polymers were higher than that of the corresponding linear analogues. All the polymers showed nematic phase (nematic droplets) over a broad temperature range. The effect of kinked structural unit on photoresponsive property is less in both linear and hyperbranched architectures. Although the effect of architectural nature is highly considerable within the hyperbranched architectures, the polymer (HPE–33) synthesized by A₃ + B₃ approach showed highest rate of photocrosslinking, followed by HPE–I 32; HPE–T 32, and HPE–23, which were synthesized by A₃ + B₂ and A₂ + B₃ approaches, respectively. The findings in photoresponsive properties were further supported by molecular modeling studies. Substantial variation of refractive index (0.015–0.024) indicates that these polymers could be used for optical recording. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Radiation chemical studies of protein reactions: Effect of radiation on the breaking of secondary bonding in protein

The effect of radiation on the breaking of secondary bonding in protein was studied by measuring the viscosity change at different radiation doses and urea concentrations. An experimental equation for the viscosity change was obtained, and the observed behavior was explained on the basis of the molecular mechanism. The general equation for the viscosity change is given by η_red = A(X ? Be^?kx) + C log R, where η_red is the reduced viscosity of the solution, R is the dose of γ-radiation, X is the concentration of urea, and A, B, C, and k are adjustable constants.     

Manipulation of the molecular weight and branching structure of hyperbranched poly(arylene ether phosphine oxide)s prepared via an A2 + B3 approach

A series of hyperbranched poly(arylene ether phosphine oxide)s (HB PAEPOs) were prepared via an A₂ + B₃ polymerization scheme with tris(4‐fluorophenyl)phosphine oxide as B₃, and a variety of bisphenols as A₂. The effects of the reactivity of the A₂ monomer, the A:B ratio, the addition mode, the solvent, and the concentration on the final molecular weight, polydispersity index (PDI), and degree of branching (DB) were studied. Soluble HB PAEPOs with weight‐average molecular weights of up to 299,000 Da were achieved. Reactions in which the A₂ component was added slowly resulted in lower DBs (0.2–0.5), whereas the slow addition of the B₃ component provided samples with DBs of approximately 0.75. Reactions performed under high‐dilution conditions afforded completely soluble materials with weight‐average molecular weights of 9000–12,100 Da and PDI values as low as 2.20. The molecular weights achieved under high‐dilution conditions were independent of the mode of monomer addition. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3871–3881, 2003     

Aglycon-Disaccharide Coupling in Mithramycin Analog Synthesis

ABSTRACT

Mithramycin (1), chromomycin A₃, and olivomycin A are structurally related, antitumor agents which belong to the aureolic acid family of antibiotics.¹ Considerable research on the synthesis of both the aglycon^2-4 and carbohydrate^7-9 portions of these molecules naturally has led to interest in methods for joining carbohydrate and aglycon units together.¹⁰ One type of coupling which is required for aureolic acid synthesis is that of the A-B disaccharide to the phenolic hydroxyl group at C-6.¹¹ In this communication such a process is described along with a flexible procedure for the formation of the protected A-B disaccharide used in the coupling process.     

Conformational behavior of nylon 6 in mixed solvents

The intrinsic viscosity [η], Huggins constant (K_H), laser light scattering, UV and IR measurements of Nylon 6 are made in m‐cresol and its mixture with 1,4‐dioxane at 20–60 °C. The intrinsic viscosity, R_g, A₂, (<S>²)^1/2 (calculated from viscosity data), R_H, and UV absorbance initially increase and then decrease with the rise in 1,4‐dioxane contents. The K_H and the transmittance of ? OH group in IR spectra show an opposite trend to that of [η]. The dielectric constant calculated from the refractive index of the solvent (m‐cresol with 1,4‐dioxane) and polymer solution shows a continuous decrease with the amount of 1,4‐dioxane. Activation energy shows a minimum while linear expansion coefficient (α³) maximum with the addition of 1,4‐dioxane. Change in [η], K_H, and other characteristics of the polymer solutions with alterations in solvent composition and temperature are the result of variation in the thermodynamic quality of the solvent, its selective adsorption, hydrogen bonding, and conformational transitions. It has been concluded that the addition of 1,4‐dioxane first enhances the quality of the solvent, encourages hydrogen bonding, and specific adsorption, and then deteriorates, bringing conformational transitions in the polymer molecules. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 534–541, 2005     

Hydrodynamic Properties and Unperturbed Dimensions of Polydecahydro- β -naphthyl and Poly- β-naphthyl Methacrylates in Different Solvents

Abstract

Intrinsic viscosity, sedimentation, light-scattering, and osmotic-pressure measurements have been carried out at 25° on dilute solutions of polydecahydro-β -naphthyl meth-acrylate (PDNa) and of poly-β-naphthyl methacrylate (PNa). For both polymers, the degree of polydispersity was around 1.5 and the molecular weight range was large: 10⁵ to 3 × 10⁶. Relations between [η], [S₀], A₂, and molecular weight have been established.

The applicability of the different theories (Stockmayer-Fixman, Kurata-Stockmayer, Fox-Flory, Cowie, Berry, Kamide-Moore) for the determination of the unperturbed dimensions from the viscosity data is discussed; Berry's relation best fits the experimental data.

These dimensions, calculated from the sedimentation data according to the Cowie-Bywater relation, agree with those obtained by viscosity. The flexibility factor is 2.9 for PDNa and 3.1 for PNa. These large values are a consequence of the presence of very bulky groups in the side chain; however, the higher η value for PNa led to the assumption that a specific interaction between the aromatic rings influences the rigidity of the main chain.     

A comparison study on Raman scattering properties of α- and β-MnO2

In this comment to a recent paper [Anal. Chim. Acta 585 (2007) 241-245], we report a comparison study on Mn oxide-related compounds with different crystallographic forms, which distinguish between β-MnO₂ and α-MnO₂ type materials via Raman scattering (RS) spectroscopy. The tetragonal rutile-type β-MnO₂ is characterized by a RS band at ∼667 cm⁻¹ of symmetry A_1g, whereas the α-MnO₂ type materials feature two main RS contributions at about 574 and 634 cm⁻¹, belonging to A_g spectroscopic species of a tetragonal hollandite-type framework. These data represent a clear signature for identifying β-MnO₂ and α-MnO₂ type materials via RS spectroscopy.     

Solution properties and chain conformation characteristics of cellulose tricarbanilate

Fractions of two cellulose tricarbanilate samples were characterized by light-scattering (weight-average molecular weight, second virial coefficient, mean-square radius of gyration), gel permeation chromatography (polydispersity index), and viscometry (intrinsic viscosity) in tetrahydrofuran and acetone. The intrinsic viscosity data were analyzed in terms of the theory developed for the continuous wormlike cylinder model, and the chain parameters (Kuhn statistical segment length λ^?1, chain diameter d, and shift factor M_L) were evaluated. The molecular-weight dependence of the mean-square radius of gyration in tetrahydrofuran was calculated for the Kratky—Porod chain model and compared with the experimental results. Data on the intrinsic viscosity and radii of gyration for other solvents at temperatures from 0 to 100°C were analyzed in the same way, and the effects of solvent and temperature on the statistical segment length were evaluated. Polymer—solvent interaction parameters were estimated from the second virial coefficients.     

Transition metal dichalcogenides (MoS2, MoSe2, WS2 and WSe2) exfoliation technique has strong influence upon their capacitance

Transition metal dichacogenides (TMD) represent an important class of layered compounds which are gaining lately an enormous interest in electrochemistry. Exfoliation of TMD materials to obtain single to few layer sheets is generally obtained through the intercalation of organolithium compounds. Here we investigated and compared the capacitive behavior of four representative TMD materials, i.e. MoS₂, MoSe₂, WS₂ and WSe₂ exfoliated with different organolithium intercalators, such as methyllithium (Me-Li), n-butyllithium (n-Bu-Li) and tert-butyllithium (t-Bu-Li). We found that both the metal/chalcogen composition and the type of intercalator strongly affect the capacitance of the exfoliated materials. These findings shall have profound implications on the construction of high-performance energy storage devices based on TMD.